Manufacture of intermediate oxidation products and apparatus therefor



. 1926 2 Sheets-Sheet Dec. 15, 1931. J. H. JAMES MANUFACTURE OFINTERMEDIATE OXIDATION PRODUCTS AND APPARATUS THEREFOR Original FiledJan, 18

Dec. 15, 1931. J, H, JAMES 1,836,326

MANUFACTURE OF INTERMEDIATE OXIDATION PRODUCTS AND APPARATUS THEREFOROriginal Filed Jan. 18, 1926 2 Sheers-She f 2 lNV ENTOR Patented Dem 15,1931 I urn STATES PATENT ounce o'osnrn HIDY JAMES, or PITTSBURGH,rnnnsYLvAniA, AssIenon To CLARENCE I.

' BYBNES, TRUSTEE, or sEwIcKLnY, PENNSYLVANIA,

MANUFACTURE or INTERMEDIATE OXIDATION rnonUcTs AND APPARATUS THEREFOROriginal application filed January 18, 1926, Serial No. 81,963.Divided'and this application filed August 10,

i I 1927.. Serial No. 212,103; g

This invention relates to the manufacture of intermediate oxidationproducts and is a division of my copending application Serial l lo.81,963, filed January 18th, 1926.

In said application, Serial No. 81,963, I have disclosed a process andapparatus for the manufacture of intermediate oxidation products fromorganic bodies, such as hydrocarbons or hydrocarbon derivatives,by theuse of a solid oxidant material which will yield oxygen to the organicbody under elevated temperature conditions. i

In a number of my copending applications, for example, Serial No.272,567, filed J anuary 22nd, 1919; Serial No. 281,124, filedMarclr'l'th, 1919; Serial No.'335,937,'filed November 5th, 1919; SerialNo. 435,355,filed January 6th, 1921 and SerialNo. 520,283, filedDecember 6th, 1921; I have disclosed processes for making intermediateoxidation products from mineral hydrocarbons such as petroleum orfractions thereof, the products from the low temperature distillationofcoals and from shale oil, whether.or" notsaid products have been crackedprior to'oxidation. In these several processes thehydrocarbon in vaporor gaseous phase is mixed with oxygen or an oxygen containing ,gas suchas air, and the mixture is passed througha reactionlzone at atemperature between 160 and 500 C. with or' without a catalyst. Thecondensed products of such process are in the range from'aliphaticalcohols to hydroxylated aldehyde acids, including alcohols, aldehydes,aldehyde alcohols, esters, ketones,etc. I

Such processes, while generally applicable are particularly desirablefor liquid hydrocarbonshaving a boiling range from that of kerosene'through the mineral oil fractions ofheavier'molecular Weights. -Wherefractions lighterthan the lower kerosene-limit, including gaseoushydrocarbons, are used, the diluting effectof the nitrogen in the airmakes it difficult to procure and recover the product. Furthermore,whfere'-'these lighter hydrocarbons are used, the explosive range, whenmixed with air, is quite wide and this increases the working'hazard.

-' Byusing a'solid oxidant material as decation Serial No. 81,963, abovereferre carbon or hydrocarbon derivative. The mathrough a portion of thescreen or screens at ample,'a vapor or gaseous phase. The operation ispreferably carried out in an, at-

mosphere free, or substantially free, of air,

or free oxygen, and at a reactive temperature which will cause oxygen topass from the oxygen containing material into the hydroterial, afterbeing thus'partiallyor wholly deoxidized, is withdrawn from the reactionzone and maybe regenerated by reoxidation and thenreus'ed in theprocess.

Where, as in the present preferred form of '5 apparatus a movablecarrier is provided with an oxidantscreen or screens and the carrieractuated either continuously'or intermittently, and'the hydrocarbonstream is passed a temperature within the reactive range the usedoxidant is preferably reoxidized in other parts of its path, preferablyby subjecting it to heated air and keeping it heated in the presence ofair, before such portions again pass within the reaction Zone. I

In the preferred form the operation is I cyclic as in one passage only aportion of the hydrocarbon-will be partially oxidized. The vapor streamwill then pass through a condensing, scrubbing and washing system toextract-the partial oxidation products. The remainder of the exitstream'will then again pass through a reaction zone and the oxidizingoperation be repeated using either the same apparatus or anotherapparatus of similar type. Fresh hydrocarbon is preferably supplied tothe exit stream after extraction of products, and I usually prefer toalsotap out a portion of the remaining gaseous'stream and supply freshhydrocarbon suflicient to replace both the tapped out portion and therecovered portion converted intoproducts before repeating the processeitherin the same or a similar apparatus.

diagram of the vperiodic series beginning on the descending side of thethird peak and extending. on the descending side of the fourth peak andthe descending side of further peaks later developed. This classincludes the folvlowing metals: titanium, vanadium, chromium, manganese,zirconium, niobium, molybdenum, tantalum, tungsten and uranium. Anexcellent oxidant for my present purposes consists ofthe tri-oxide ofmolybdenum. I prefer to employ the complex oxides of metals having avarying valence. The parts of the complex'may consist of oxides ofthesame -metal or of diiferent metals. Such complexes may be regarded assalts, that is, compounds ofone or more basic acid oxides. The'basic andacid parts of these complexes may be formed from oxides of differentmetals, in which case each metal or group of metals used should possessvarying valence. The basic oxides may be the lower oxides of the metals:in'the class named or may be the oxides of iron, copper, nickel,lanthanum, cobalt, thori um or eight or nine rare earth metals. In bothacid or basic portions there may, of .course, be two or more of thesecombined. I may use chromic-chromate, tungsten-tungstate, etc.. forexample.

' It will be noted that in my new method andapparatus the hydrocarbon orhydrocarbon derivative is in finely divided form, preferably in thevapor or gaseous phase, while the oxygen is derived from a materialcontaining chemically-combined oxygen and preferably in solid finelydivided condition. The temperature will vary according to thehydrocarbon or hydrocarbon mixture being treated. Under the conditionsnamed, the hydrocarbon can be partially oxidized to form intermediateproducts, such as alcohols, aldehydes and acids. During the process, ifa solid oxideis employed, the oxide will pass to a lower state ofoxidation, or to the metal -itself.. i V My application'Seria-l No.81,963 describes various forms of apparatus effective for bringing thehydrocarbon or hydrocarbon de- :ri'vative into the desired intimatecontact with the solid oxidant. The present invention-specificallycovers an embodiment of the broad invention wherein the solid oxidant is50 are secured.

into the treating station.

pads which are moved inanorbitalpath so as to bring them into the pathof the hydrocarbon or hydrocarbon derivative, and thereafter into aregenerating zone where they are reoxidized. 1

In the accompanying drawings, illustrating the present preterredembodiment of this type of apparatus,

I Figure 1 is aside elevation partly broken away or of one form ofapparatus which may be used, I Figure 2 is an'end elevation of theapparatus shown inFigure .1,

' Figure 3 is a vertical transverse section taken on the line IIIIII ofFigure 1.

Figure 4 a horizontal transverse section 7 taken on the line IVIV ofFigure 1, and '7 Figure 5 is a vertical transverse section taken on theline V-V of Figure 1. i

In the illustrated embodiment ofthe invention, the oxidant is carried bypervious screens 50. In a complete cycle of the process thehot vapors orgases to be treated are passed through a pador screen 50, and-are thusoxidized, after which the pad is again supplied with oxygen bysubjecting it to heated air. In order to carry out these steps I providea heating chamber 51. divided into two compartments 52-ancl 53 by awheel 54.- provided adjacent the rim with a series of openings 50a, intowhichthe screens or pads fits into a recess 55 which acts as a seal sothat substantially the only communication between. the portions 52 and53 ofthe chamber is through the screens 50. Hot air is supplied to thechamber 52 through a conduit 56 at one side and below and this airpasses through the screens'50 and finds an outlet through a stackreoxidizes the oxidant screens for the next treatment of'the hydrocarbonvapor, gas or station by rotating the wheel 54. In Figure 1 there isshown a motor 58connected to the shaft 59 of the wheel through suitablegearing 60 for causing rotation of the wheel at any desired speed.

The heated vapor issupplied from a conduit 61-havinga downwardlyextending portion 62 and a horizontal portion 63 extending Theconstruction is shown in detail in Figures 4: and 5. The conduit 63terminates in a contact member 64 which terminates in a cheek platej65and is slidably mounted in the frame 66.

The cheek plate 65 fits into an annular in whichithe pads 50 are fittedterminate in the recess. The contact member Beds pro- The periphery ofthe wheel I 57 at the other side of the top. The hot air 3105 recess 6'?in the wheel 51- and-it will be noted from Figures 3 and that theopenings 50a vided with an opening 64a adapted to register with one ofthe openings 50a, while the cheek plates 65 extend vertically so as tocover the adjacent openings 50a and thus prevent any leakage ofhydrocarbon vapors from the con The contact member 64: is duplicated onthe other side of the wheel, this being indicated in Figures 4 and 5 at64. The contact memloer 64 is' provided with a cheek plate 65 which iscoextensive with the cheek plate 65, as best shown in Figure 5.

In operation the vapors to be treated enter through the pipe 63, passthrough one of the screens 50 and leave the treating station through aconduit 7 2. The conduit 72 leads into a downwardly extending conduit 73 conpected to an outlet 7 4 through a swivel joint It will be notedthat thearrangement of inlet and outlet conduits is such that there is ageneral downflow of the vapors at all times, so that no condensedhydrocarbons cancollect anywhere in the apparatus. As shown in Figure 5the openings through the contact members 64 and 64 are so arranged thatcondensed vapors cannot collect therein.

The frame 66 is slidably mounted in a guide 7 6 built into the furnacewall to permit movement of such frame toward or away from the center ofthe furnace with expansion or contraction of the wheel. In apparatus ofthis character the variation in wheel diameter will be a material amountand the arrangement shown prevents jamming of the apparatus. The frame66 is provided with interior flanges 77 which are packed to preventleakage. With the movement of the frame 66 inwardly or outwardly, it isofcourse necessary to move the conduits 63 and 72 correspondingly andthe swivel joint 75, together with a similar swivel joint (not shown) onthe conduit 61, make this movement possible.

Packings 7 8 are provided on the contact members 64 and 64 for theconduits 63 and 72 so that expansion longitudinally of these con-- duitsmay be provided for while maintaining a tight joint and at the same timepermit the slight rotation of the conduits which will be occasioned on amovement of the frame 66.

The wheel illustrated in the drawings has been shown as continuouslyrotated, but it.

will be understood that a Geneva movement .Monel metal.

traction.

if desired. As shown in Figure 7, the screens 50are'separated from oneanother only a relatively short distance and when so varranged thecontinuous rotation is advantageous, The treating chamber is'maintainedat suitable temperature by the hot air entering through the opening 56and the treating station T is so located with respect to the openings 56and 5.7 that it will be suitably heated without any undue pressuredifferential, which would tend to causeleakage, existingat that pointThe wheel proper may be made. of any suitable material such as castiron, but it is desirable to make the rim of a close-grained metalwhichwill take a high polish and will not be subject; to warping, such'as nichrome, invar, or The contact members 64 and 64 should be made of'material which is not subject to warping and preferably has a low,coefficient of expansion and con- The temperature in the reaction zoneis preferably below 600-700 C. and will vary with the material treated,being often as low as,160170 C. for example with olefin gases .or--those containing unsaturated compounds. Methane or fixed gases usuallyneed highertemperatures than vaporized liquids. The temperature forregenerating or revivifying the oxidant is usually. higher than that inthe reaction zone. A short time of sojourn or contact is preferable toavoid secondary reactions. The process may be used with any kinds ofhydrocarbons or hydrocarbon derivatives or compounds, whether aliphatic,aromatic, naphthenicor otherwise.

[The process may be carried out either at atmospheric, sub-atmospheric,or super-atmospheric pressures. I do notclaim herein the metallurgicalmethod of reducing metallic oxides to. metals herein disclosed, as thatinvention is covered in the claims of my 00- pendin r divisionalapplication Ser. No. 550,-

ing relative movement between the carrier and said connections and meansfor revivifying said oxidant material exterior to said reactive zone. 7

2. Inchemical apparatus, a movable carrier arranged to support dividedsolid oxidantmaterial, means for moving the carrier, a reactive zoneenclosure coacting with a portion of the carrier and connections forpassing a chemical in gaseous phase to the reactive zone, and means forsupplying heat to and revivifying the oxidant exterior to the enclosure.7

In chemical apparatus, an endless car rier arranged to support dividedsolid oxidant material, means for moving the carrier in a continuousmanner, a reactive zone enclosure coacting With a portion of the carrierand connections for passing a chemical in gaseous phase to the reactivezone, and means for supplying heat to and 'revivifying the oxidantexterior to the enclosure.

$111 the method of making organic compounds, the steps consisting offeeding a' stream of an organic compound through an enclosed reactivezone, bringing it in said zone into contact With a supported layer oi asolid chemical compound capable of releasing a reactive gas, maintainingconditions in the zone'to cause release of said reactive gas from thelayer, causing relative movement to expose successive portions of thesolid chemical compound to the stream, and revivifying successiveportions of the'solid compound While retained in the support.

5. In chemical apparatus, an enclosed reactive zone, means for applyingheat thereto, a support extending through the zone and arranged toreceive a layer of a solid chemical compound capable of releasing areactive gas under the zone conditions, connections arranged to feed achemical in finely divided form through the enclosed reactive zone, andmeans for causing relative movement between the support and zoneto'bring fresh portions of the solid chemical compound into contact Withthat finely divided chemical' passing through the zone.

In testimony whereof I have hereunto set my hand. 7

JOSEPH HIDY JAMES.

